Olefin polymerization catalysts are of great use in industry. Hence, there is interest in finding new catalyst systems that increase the commercial usefulness of the catalyst and allow the production of polymers having improved properties.
Catalysts for olefin polymerization are often based on transition metal compounds as catalyst precursors, which are activated either with an alumoxane or with an activator containing a non-coordinating anion. A typical catalyst system includes a metallocene catalyst and an activator, and an optional support. Many metallocene catalyst systems can be used in homogeneous polymerizations (such as solution or supercritical) and supported catalyst systems are used in many polymerization processes, often in slurry or gas phase polymerization processes.
WO 2004/013149 A1 discloses group 4 metal constrained geometry complexes of tricyclic 4-aryl substituted indenyl ligands, esp. 1,5,6,7-tetrahydro-4-aryl-s-indacen-1-yl ligands, where the tetrahydro-s-indacene is substituted in the 4 position with a C6-12 aryl group, and is preferably not substituted in the 5, 6, or 7 position, and if substituted in the 5, 6, or 7 position, is substituted by at most only one substituent at each position.
U.S. Pat. No. 6,420,507 discloses substituted tetrahydro-s-indacenyl transition metal complexes (such as Examples H to N), where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position and is substituted in the 2 and/or 3 position.
EP 1 120 424 (and family member U.S. Pat. No. 6,613,713) disclose tert-butylamino-2-(5,6,7-tetrahydro-s-indacenyldimethylsilyl) titanium dichloride indenyl ligands as polymerization catalyst where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position.
WO 2001/042315 discloses dimethylsilylene(t-butylamido)(2-methyl-tetrahydro-s-indacenyl)Ti(CH2SiMe3)2 (see examples 27 and 28, and compounds IB5 and IB5′ in claim 21) as polymerization catalysts where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position.
WO 98/27103 discloses dimethylsilylene(t-butylamido)(2-methyl-tetrahydro-s-indacenyl)TiCl2 (see example 1) and others as polymerization catalysts where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position.
Tuor, et al. (Journal of the American Chemical Society 136 (36), 12794-12798 (2014)) disclose Mono- and trinuclear sumanenyl zirconocene complexes Cp(sumanenyl)ZrCl2, Cp*(sumanenyl)ZrCl2, and (C21H9)[(Cp*)ZrCl2]3.
Kociolek, et al. (Tetrahedron Letters (1999), 40(22), 4141-4144) discloses flash vapor pyrolysis tetrahydro[as]-indacene ligand.
Other references of interest include: U.S. Pat. No. 5,382,630; U.S. Pat. No. 5,382,631; U.S. Pat. No. 8,575,284; U.S. Pat. No. 6,069,213; Kim, J. D. et al., J. Polym. Sci. Part A: Polym Chem., 38, 1427 (2000); Iedema, P. D. et al., Ind. Eng. Chem. Res., 43, 36 (2004); U.S. Pat. No. 6,656,866; U.S. Pat. No. 8,815,357; US 2014/0031504; U.S. Pat. No. 5,135,526; U.S. Pat. No. 7,385,015; WO 2007/080365; WO2012/006272; WO2014/0242314; WO 00/12565; WO 02/060957; WO 2004/046214; U.S. Pat. No. 6,846,770; U.S. Pat. No. 6,664,348; WO 05/075525; US 2002/007023; WO 2003/025027; US 2005/0288461; US 2014/0031504; U.S. Pat. No. 8,088,867; U.S. Pat. No. 5,516,848; U.S. Pat. No. 4,701,432; U.S. Pat. No. 5,077,255; U.S. Pat. No. 7,141,632; U.S. Pat. No. 6,207,606; U.S. Pat. No. 8,598,061; Polymer Engineering and Science-2007, DOI 10.1002/pen, pages 131-139, published online in Wiley InterScience (www.interscience.wiley.com) 2007 Society of Plastics Engineers; US 2012/0130032; U.S. Pat. No. 7,192,902; U.S. Pat. No. 8,110,518; U.S. Pat. No. 9,193,856; U.S. Pat. No. 7,355,058; U.S. Ser. No. 62/149,799, filed Apr. 20, 2015 (and all cases claiming priority to or the benefit of U.S. Ser. No. 62/149,799); U.S. Ser. No. 62/103,372, filed Jan. 14, 2015 (and all cases claiming priority to or the benefit of U.S. Ser. No. 62/103,372); and PCT/US2015/067582, filed Dec. 28, 2015.
There is still a need in the art for new and improved catalyst systems for the polymerization of olefins, in order to achieve increased activity or specific polymer properties, such as high melting point, high molecular weights, to increase conversion or comonomer incorporation, or to alter comonomer distribution without deteriorating the resulting polymer's properties.
It is therefore also an object of the present invention to provide novel supported catalysts systems and processes for the polymerization of olefins using such catalyst systems.
The metallocene compounds and catalyst systems described herein address these needs by producing highly active catalysts containing a higher comonomer incorporation and molecular weight, that when formed into a molded part has improved properties (such as improved strength).